Patent application title: SURFACE-ENHANCED RAMAN SCATTERING SUBSTRATE AND RAMAN DETECTING SYSTEM HAVING THE SAME

Abstract:

A surface-enhanced Raman scattering substrate includes a carbon nanotube
film structure and a plurality of metallic particles disposed on the
carbon nanotube film structure. The carbon nanotube film structure
includes a number of carbon nanotubes joined by van der Waals attractive
force therebetween. The carbon nanotube film structure is a free-standing
structure.

2. The substrate of claim 1, wherein the carbon nanotube film structure is
a free-standing structure.

3. The substrate of claim 1, wherein the carbon nanotube film structure is
isotropic and the carbon nanotubes therein are entangled with each other.

4. The substrate of claim 1, wherein the carbon nanotubes are
substantially parallel to a surface of the carbon nanotube film
structure.

5. The substrate of claim 4, wherein the carbon nanotubes are
substantially aligned in a single direction and joined end to end by the
van der Waals attractive force therebetween.

6. The substrate of claim 1, further comprising a plurality of stacked
carbon nanotube film structures, wherein adjacent carbon nanotube film
structures are adhered by the van der Waals attractive force
therebetween.

7. The substrate of claim 1, wherein the carbon nanotubes are
substantially perpendicular to a surface of the carbon nanotube film
structure.

8. The substrate of claim 1, further comprising a framing element, wherein
a part of the carbon nanotube film structure is attached to the framing
element, and another part of the carbon nanotube film structure is
suspended.

9. The substrate of claim 1, wherein interparticle gaps are formed among
the particles, each of the interparticle gaps is about 1 nanometer to
about 15 nanometers.

10. The substrate of claim 9, wherein each of the interparticle gaps is
about 2 nanometers to about 5 nanometers.

11. The substrate of claim 1, wherein each of the metallic particles has a
diameter of about 1 nanometer to about 50 nanometers.

12. The substrate of claim 11, wherein the diameter of each of the
metallic particles is about 18 nanometers to about 22 nanometers.

13. The substrate of claim 11, wherein the diameter of each of the
metallic particles is about 3 nanometers to about 7 nanometers.

14. The substrate of claim 1, wherein the carbon nanotube film structure
further comprises transition layers disposed between the carbon nanotubes
and the metallic particles to provide a smooth surface for disposing the
metallic particles.

15. The substrate of claim 14, wherein the transition layer has a
thickness of about 1 nanometer to about 50 nanometers.

16. The substrate of claim 15, wherein the thickness of the transition
layer is about 3 nanometers to about 7 nanometers.

17. A surface-enhanced Raman scattering substrate, comprising:a carbon
nanotube film structure;a transition layer disposed on a surface of the
carbon nanotube film structure; anda metallic layer disposed on a surface
of the transition layer opposite to the carbon nanotube film
structure;wherein the carbon nanotube film structure comprises a
plurality of carbon nanotube films, each of the carbon nanotube film
comprises a plurality of carbon nanotubes substantially orienting along a
preferred orientation and substantially parallel to a surface of the
corresponding carbon nanotube film, and aligned directions of adjacent
carbon nanotube films is substantially perpendicular to each other.

18. The substrate of claim 17, wherein the metallic layer consists of a
plurality of metallic particles.

19. The substrate of claim 17, wherein the metallic layer has a thickness
of about 1 nanometer to about 50 nanometers.

20. A Raman detecting system, comprising:a surface-enhanced Raman
scattering substrate comprising a carbon nanotube film structure and a
plurality of metallic particles disposed on the carbon nanotube composite
film;a projecting module projecting a beam of light to the substrate;
anda receiving module collecting the light scattered by the
substrate;wherein the carbon nanotube film structure comprises a
plurality of carbon nanotubes joined by van der Waals attractive force
therebetween.

Description:

CROSS-REFERENCE

[0001]This application claims all benefits accruing under 35 U.S.C.
§119 from China Patent Application No. 200910190213.4, filed on Sep.
15, 2009 in the China Intellectual Property Office, the disclosure of
which is herein by reference. This application is related to copending
applications entitled, "RAMAN DETECTING SYSTEM AND METHOD FOR USING THE
SAME", filed ______ (Atty. Docket No. US27186).

BACKGROUND

[0002]1. Technical Field

[0003]The present disclosure generally relates to SERS (surface-enhanced
Raman scattering) substrates, particularly, an SERS substrate based on
carbon nanotubes, and a Raman detecting system having the same.

[0004]2. Description of Related Art

[0005]Fabrication of a stable SERS substrate with high enhancement has
been a focus because it is a precondition for the study of SERS effect. A
typical SERS substrate is usually composed of rough metal surface or
coupled metal particles. In a paper entitled, "Electrochemical deposition
of silver nano-particles in multi-walled carbon nanotube-alumina-coated
silica for surface-enhanced Raman scattering-active substrates," by Tsai
Yu Chen et al, Electrochemistry Communications, 2009, 11, 542-545, an
SERS substrate based on carbon nanotubes was proposed. The SERS substrate
can be fabricated by means of a wet-state process and depositing Ag
particles on a multi-walled carbon nanotube (MWCNT) alumina-coated silica
film. However, the wet-state dispersion of carbon nanotubes includes
chemical treatments, which usually leads to some defects and low usage of
carbon nanotubes.

[0006]What is needed therefore is a stable and cost-effective SERS
substrate based on carbon nanotubes.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007]Many aspects of the embodiments can be better understood with
references to the following drawings. The components in the drawings are
not necessarily drawn to scale, the emphasis instead being placed upon
clearly illustrating the principles of the embodiments. Moreover, in the
drawings, like reference numerals designate corresponding parts
throughout the several views.

[0008]FIG. 1 is a schematic structural view of one embodiment of a Raman
detecting system.

[0017]FIG. 10 shows a high magnification TEM image of the SERS substrate
in FIG. 9.

[0018]FIG. 11 shows a comparison of Raman spectra of the CNT grid, the
Ag-CNT grid and the Ag--SiO2-CNT grid.

[0019]FIG. 12 shows a comparison of Raman spectra of aqueous pyridine on
the CNT grid, the Ag-CNT grid, and the Ag--SiO2-CNT grid.

[0020]FIG. 13 shows comparison of Raman spectra of R6G on the CNT grid,
the Ag-CNT grid, and the Ag--SiO2-CNT grid.

[0021]FIG. 14 is a schematic structural view of one embodiment of a Raman
detecting system.

[0022]FIG. 15 is a schematic structural view of one embodiment of an SERS
substrate.

[0023]FIG. 16 shows a comparison of Raman spectra of R6G on an MWCNT array
and an Ag-MWCNT array.

[0024]FIG. 17 shows a comparison of Raman spectra of R6G on an SWCNT array
and two Ag-SWCNT arrays with different thicknesses of silver film.

DETAILS DESCRIPTION

[0025]The disclosure is illustrated by way of example and not by way of
limitation in the figures of the accompanying drawings in which like
references indicate similar elements. It should be noted that references
to "an" or "one" embodiment in this disclosure are not necessarily to the
same embodiment, and such references mean at least one.

[0026]Referring to FIG. 1 of an embodiment, a Raman detecting system 100
includes a projecting module 110, a surface-enhanced Raman scattering
(SERS) substrate 120, and a receiving module 130.

[0027]The projecting module 110 is configured to project a beam of light
to the SERS substrate 120 to form a scattering light. Acreage of a cross
section of the beam of light on the SERS substrate 120 can be less than
or equal to 2 square millimeters. The projecting module 110 can include a
light source such as argon laser. The light source can have a narrower
frequency width. The beam of light can have a wavelength of about 450.0
nanometers to about 514.5 nanometers. In one embodiment, the wavelength
of the beam of light is about 514.5 nanometers. More scattering light can
be obtained by the beam of light with the wavelength of about 514.5
nanometers.

[0028]The receiving module 130 is configured to collect the scattering
light scattered by the SERS substrate 120 to form a Raman spectra figure
of a sample adhered on the SERS substrate 120. The receiving module 130
can include a multi-channel photon detector such as a charge coupled
device (CCD), or a single-channel photon detector such as a
photomultiplier. Details of vibration modes of the sample can be read
from the Raman spectra figure formed by the receiving module 130.

[0029]The SERS substrate 120 is configured to load the sample. The sample
can be directly adhered to the SERS substrate 120. The sample can be a
solid sample or a liquid sample. The solid sample can be sample powders,
or particles adhering sample thereon. The liquid sample can be drops
dissolving the sample therein, or molten sample. When the SERS substrate
120 is irradiated by the beam of light, a part of the beam of light can
strike the sample to form the scattering light. Specifically, some
photons of the beam of light can strike the sample and collide with
molecules of the sample, thus, the momentum or the frequency of the
photons can be changed. The variation of the frequency of the photons can
correspond to variation frequencies of chemical bonds in the molecules of
the sample. Thus, the molecular structure can be read from the scattering
light.

[0030]The SERS substrate 120 can include a supporting element 121 and a
carbon nanotube composite film 122.

[0031]The supporting element 121 is configured to support or fix the
carbon nanotube composite film 122. The supporting element 121 can be a
transparent substrate such as a glass panel, a plastic substrate, or a
framing element such as a grid framework. Thus, less beams of light can
be reflected by the substrate to disturb the scattering light. If the
supporting element 121 is a transparent substrate, the carbon nanotube
composite film 122 can be disposed on a surface of the transparent
substrate directly. If the supporting element 121 is a framing element,
the carbon nanotube composite film 122 can be suspended on the framing
element. The area of the suspended part of the carbon nanotube composite
film 122 can be greater than the cross-sectional area of the beam of
light on the SERS substrate 120.

[0032]The carbon nanotube composite film 122 can include a carbon nanotube
film structure and a metallic film disposed on the carbon nanotube film
structure. The carbon nanotube film structure is capable of forming a
free-standing structure. The term "free-standing structure" can be
defined as a structure that does not have to be supported by a substrate.
For example, a free-standing structure can sustain the weight of itself
when it is hoisted by a portion thereof without any significant damage to
its structural integrity. The free-standing structure of the carbon
nanotube film structure is realized by the carbon nanotubes joined by van
der Waals attractive force. So, if the carbon nanotube film structure is
placed between two separate supporters, a portion of the carbon nanotube
film structure, not in contact with the two supporters, would be
suspended between the two supporters and yet maintain film structural
integrity. Simultaneously, the supporting element 121 is an optional
structure and can be omitted, if the carbon nanotube film structure is a
free-standing structure.

[0033]The carbon nanotube film structure includes a plurality of carbon
nanotubes uniformly distributed therein, and joined by van der Waals
attractive force therebetween. The carbon nanotubes in the carbon
nanotube film structure can be orderly or disorderly arranged. The term
`disordered carbon nanotube film structure` includes, but is not limited
to, a structure where the carbon nanotubes are arranged along many
different directions, such that the number of carbon nanotubes arranged
along each different direction can be almost the same (e.g. uniformly
disordered), and/or entangled with each other. `Ordered carbon nanotube
film structure` includes, but is not limited to, a structure where the
carbon nanotubes are arranged in a consistently systematic manner, e.g.,
the carbon nanotubes are arranged approximately along a same direction
and or have two or more sections within each of which the carbon
nanotubes are arranged approximately along a same direction (different
sections can have different directions). The carbon nanotubes in the
carbon nanotube film structure can be single-walled, double-walled,
and/or multi-walled carbon nanotubes.

[0034]Macroscopically, the carbon nanotube film structure may have a
substantially planar structure. The planar carbon nanotube structure can
have a thickness of about 0.5 nanometers to about 100 microns. The carbon
nanotube film structure includes a plurality of carbon nanotubes and
defines a plurality of micropores having a size of about 1 nanometer to
about 500 nanometers. The carbon nanotube film structure includes at
least one carbon nanotube film, the at least one carbon nanotube film
including a plurality of carbon nanotubes substantially parallel to a
surface of the corresponding carbon nanotube film.

[0035]The carbon nanotube film structure can include a flocculated carbon
nanotube film as shown in FIG. 2. The flocculated carbon nanotube film
can include a plurality of long, curved, disordered carbon nanotubes
entangled with each other and can form a free-standing structure.
Further, the flocculated carbon nanotube film can be isotropic. The
carbon nanotubes can be substantially uniformly dispersed in the carbon
nanotube film. The adjacent carbon nanotubes are acted upon by the van
der Waals attractive force therebetween, thereby forming an entangled
structure with micropores defined therein. Alternatively, the flocculated
carbon nanotube film is very porous. Sizes of the micropores can be of
about 1 nanometer to about 500 nanometers. Further, due to the carbon
nanotubes in the carbon nanotube structure being entangled with each
other, the carbon nanotube structure employing the flocculated carbon
nanotube film has excellent durability, and can be fashioned into desired
shapes with a low risk to the integrity of carbon nanotube structure. The
flocculated carbon nanotube film, in some embodiments, will not require
the use of structural support or due to the carbon nanotubes being
entangled and adhered together by van der Waals attractive force
therebetween. The flocculated carbon nanotube film can have a thickness
of about 0.5 nanometers to about 100 microns.

[0036]The carbon nanotube film structure can include a pressed carbon
nanotube film. The carbon nanotubes in the pressed carbon nanotube film
can be arranged along a same direction or arranged along different
directions. The carbon nanotubes in the pressed carbon nanotube film can
rest upon each other. The adjacent carbon nanotubes are combined and
attracted to each other by van der Waals attractive force, and can form a
free-standing structure. An angle between a primary alignment direction
of the carbon nanotubes and a surface of the pressed carbon nanotube film
can be in an approximate range from 0 degrees to approximately 15
degrees. The pressed carbon nanotube film can be formed by pressing a
carbon nanotube array. The angle is closely related to pressure applied
to the carbon nanotube array. The greater the pressure, the smaller the
angle. The carbon nanotubes in the carbon nanotube film can be
substantially parallel to the surface of the carbon nanotube film when
the angle is 0 degrees. A length and a width of the carbon nanotube film
can be set as desired. The pressed carbon nanotube film can include a
plurality of carbon nanotubes substantially aligned along one or more
directions. The pressed carbon nanotube film can be obtained by pressing
the carbon nanotube array with a pressure head. Alternatively, the shape
of the pressure head and the pressing direction can determine the
direction of the carbon nanotubes arranged therein. Specifically, in one
embodiment, when a planar pressure head is used to press the carbon
nanotube array along the direction perpendicular to a substrate. A
plurality of carbon nanotubes pressed by the planar pressure head may be
sloped in many directions. In another embodiment, as shown in FIG. 3,
when a roller-shaped pressure head is used to press the carbon nanotube
array along a certain direction, the pressed carbon nanotube film having
a plurality of carbon nanotubes substantially aligned along the certain
direction can be obtained. In another embodiment, when the roller-shaped
pressure head is used to press the carbon nanotube array along different
directions, the pressed carbon nanotube film having a plurality of carbon
nanotubes substantially aligned along different directions can be
obtained. The pressed carbon nanotube film can have a thickness of about
0.5 nanometers to about 100 microns, and can define a plurality of
micropores having a diameter of about 1 nanometer to about 500
nanometers.

[0037]In some embodiments, the carbon nanotube film structure includes at
least one drawn carbon nanotube film as shown in FIG. 4. The drawn carbon
nanotube film can have a thickness of about 0.5 nanometers to about 100
microns. The drawn carbon nanotube film includes a plurality of carbon
nanotubes that can be arranged substantially parallel to a surface of the
drawn carbon nanotube film. A plurality of micropores having a size of
about 1 nanometer to about 500 nanometers can be defined by the carbon
nanotubes. A large number of the carbon nanotubes in the drawn carbon
nanotube film can be oriented along a preferred orientation, meaning that
a large number of the carbon nanotubes in the drawn carbon nanotube film
are arranged substantially along the same direction. An end of one carbon
nanotube is joined to another end of an adjacent carbon nanotube arranged
substantially along the same direction, by van der Waals attractive
force. More specifically, the drawn carbon nanotube film includes a
plurality of successively oriented carbon nanotube segments joined
end-to-end by van der Waals attractive force therebetween. Each carbon
nanotube segment includes a plurality of carbon nanotubes substantially
parallel to each other, and joined by van der Waals attractive force
therebetween. The carbon nanotube segments can vary in width, thickness,
uniformity and shape. A small number of the carbon nanotubes are randomly
arranged in the drawn carbon nanotube film, and has a small if not
negligible effect on the larger number of the carbon nanotubes in the
drawn carbon nanotube film arranged substantially along the same
direction. The carbon nanotube film is capable of forming a free-standing
structure. The term "free-standing structure" can be defined as a
structure that does not have to be supported by a substrate. For example,
a free-standing structure can sustain the weight of itself when it is
hoisted by a portion thereof without any significant damage to its
structural integrity. The free-standing structure of the drawn carbon
nanotube film is realized by the successive segments joined end to end by
van der Waals attractive force.

[0038]Understandably, some variation can occur in the orientation of the
carbon nanotubes in the drawn carbon nanotube film as can be seen in FIG.
4. Microscopically, the carbon nanotubes oriented substantially along the
same direction may not be perfectly aligned in a straight line, and some
curve portions may exist. Furthermore, it can be understood that some
carbon nanotubes are located substantially side by side and oriented
along the same direction and in contact with each other.

[0039]Referring to FIG. 5, in one embodiment, the carbon nanotube film
structure of the SERS substrate 120 consists of a plurality of stacked
drawn carbon nanotube films. The number of the layers of the drawn carbon
nanotube films is not limited, provided the thickness of the carbon
nanotube film structure can be maintained in a range from about 0.5
nanometers to about 100 microns. Adjacent drawn carbon nanotube films can
be adhered by only the van der Waals attractive force therebetween. An
angle can exist between the carbon nanotubes in adjacent drawn carbon
nanotube films. The angle between the aligned directions of the adjacent
drawn carbon nanotube films can range from 0 degrees to about 90 degrees.
In one embodiment, the angle between the aligned directions of the
adjacent drawn carbon nanotube films is substantially 90 degrees, thus a
plurality of substantially uniform micropores is defined by the carbon
nanotube film structure. If the sample adhered to the SERS substrate 120
is a liquid sample, a solvent film can be formed on the carbon nanotube
film structure due to the substantially uniform micropores. The carbon
nanotubes of adjacent drawn carbon nanotube films can overlap with each
other to define a plurality of nodes therebetween capable of
accommodating more samples therein.

[0040]The metallic film can be disposed on one surface of the carbon
nanotube film structure or on two opposite surfaces of the carbon
nanotube film structure. The metallic film can be formed by means of
depositing a metallic material on the carbon nanotube film structure by,
for example, e-beam evaporation or sputtering. A quartz crystal
oscillator can be used to monitor the film thickness. A material of the
metallic film can be noble metal or transition metal. The material of the
metallic film can be gold, silver, copper, or nickel. The metallic film
can have a thickness of about 1 nanometer to about 50 nanometers. In one
embodiment, the metallic film has a thickness of about 18 nanometers to
about 22 nanometers. In another embodiment, the metallic film with a
thickness of about 3 nanometers to about 7 nanometers can improve the
Raman enhancement factor of the SERS substrate 120. Microscopically, the
metallic film can include a plurality of metallic particles. The metallic
particles can be disposed on the outer surface of the carbon nanotubes of
the carbon nanotube film structure. Simultaneously, more metallic
particles can be disposed on the carbon nanotubes exposing out of the
carbon nanotube film structure. The metallic particles each can have a
diameter of about 1 nanometer to about 50 nanometers. A plurality of
interparticle gaps can be formed among the metallic particles. The
interparticle gap is about 1 nanometer to about 15 nanometers. In other
words, gap or space between the metallic particles can be about 1
nanometer to about 15 nanometers. In one embodiment, the interparticle
gap is about 2 nanometers to about 5 nanometers. Understandably, less
than 1 percent of the metallic particles can have a diameter of about 50
nanometers. Less than 1 percent of the interparticle gap can be greater
than 15 nanometers.

[0041]The carbon nanotubes of the SERS substrate 120 can have small
dimensions and define a plurality of uniform micropores. Thus, the
metallic particles having small size can be formed on the carbon nanotube
film structure to define a plurality of interparticle gaps with a small
size. The smaller the size of the interparticle gap, the greater the
electromagnetic enhancement and Raman enhancement factor of the SERS
substrate 120. A means for fabricating the SERS substrate 120 can be
based on a technique of depositing the metallic particles on the carbon
nanotube film structures formed by a dry-state process. Thus, a simple
dry-state method can be used for fabricating low-cost, stable and
sensitive SERS substrates 100.

[0042]The composite carbon nanotube film can further include a transition
layer inserted between the carbon nanotube film structure and the
metallic film. The transition layer can be deposited on the carbon
nanotube film structure before the evaporation or sputtering of the
metallic film. The transition layer can have a thickness of about 10
nanometers to about 100 nanometers. In one embodiment, the transition
layer has a thickness of about 15 nanometers to about 30 nanometers.
Microscopically, the transition layer can cover part or all the outer
surfaces of the carbon nanotubes of the carbon nanotube film structure.
The transition layer can provide a surface smoother than the surface of
the carbon nanotube film structure. Stresses endured by the metallic
particles in all orientations can be substantially equal to each other.
Thus, the transition layer can improve the shape regularity of the
metallic particles. The metallic particles can tend to form quasi-uniform
spheres on the transition layer and improve electromagnetic enhancement
and Raman enhancement factor of the SERS substrate 120. A material of the
transition layer can be inorganic oxide such as silicon dioxide and
magnesium oxide. In one embodiment, the transition layer is a silicon
dioxide layer with a thickness of about 20 nanometers.

[0043]The plurality of stacked drawn carbon nanotube films as shown in
FIG. 5 can be defined as a CNT grid. Referring to FIG. 6 and FIG. 7, a
SERS substrate 120 including the CNT grid and a silver film can be
provided and be defined as an Ag-CNT grid. The silver film can be
disposed on a surface of the CNT grid, and have a thickness of about 5
nanometers. An Energy Dispersive Spectrometer (EDS) image of the Ag-CNT
grid can be shown in FIG. 8. In FIG. 8, the copper is from a TEM micro
gird, thus, the elements of the Ag-CNT grid can consist of silver and
carbon. Referring to FIG. 9 and FIG. 10, an SERS substrate 120 including
the CNT grid, a silicon dioxide layer, and a silver film can be provided
and be defined as an Ag--SiO2-CNT grid. The silicon dioxide layer is
deposited on the CNT grid and the silver film is deposited on the silicon
dioxide layer. The silver film can have a thickness of about 5
nanometers. The silicon dioxide layer can have a thickness of about 20
nanometers.

[0045]The Raman spectrum of the Ag-CNT grid can indicate that the silver
nano-particles of the silver film can obviously enhance a Raman intensity
of the MWCNTs. The Raman spectrum of Ag--SiO2-CNT grid can indicate
that the silicon dioxide inserted between the silver film and carbon
nanotube film can further magnify the effect of enhancement of the SERS
substrate 120. An intensity of G peak for the Ag-CNT grid and an
intensity of G peak for the Ag--SiO2-CNT grid can be enhanced by 6.5
and 104.8 times respectively as compared to an intensity of G peak of the
CNT grid.

[0046]To test a Raman-enhancing capability of the CNT grid, the Ag-CNT
grid, and the Ag--SiO2-CNT grid, several organic molecules can be
selected for measurement by the CNT grid, the Ag-CNT grid, and the
Ag--SiO2-CNT grid respectively.

[0047]A water solution of pyridine (volume ratio of pyridine to water=1:4)
can be applied to the CNT grid and the Ag-CNT grid and the
Ag--SiO2-CNT grid respectively, and then Raman spectra of the CNT
grid and the two substrates were recorded. As shown in FIG. 12, Raman
spectrum of R6G on the CNT grid can not present the details of vibration
modes of pyridine except several peaks at 657, 1002, 1034, and 3073
cm-1 with very low intensity. In contrast, details and highly
enhanced Raman peaks can be observed for pyridine adsorbed on the Ag-CNT
grid and the Ag--SiO2-CNT grid, and can display the capability of
the Ag-CNT grid and the Ag--SiO2-CNT.

[0048]A droplet of Rhodamine 6G (R6G) ethanol solution (10-6 M) can
be used to slightly soak the surfaces of the CNT grid, the Ag-CNT grid,
and the Ag--SiO2-CNT. Raman spectra of the CNT grid and the two
substrates can be recorded after the evaporation of ethanol. As shown in
FIG. 13, highly enhanced Raman peaks can be observed for R6G adsorbed on
the Ag-CNT grid and the Ag--SiO2-CNT grid, while Raman spectrum of
R6G on the CNT grid cannot present any visible vibration modes of R6G. In
normal Raman scattering, the fluorescence of R6G usually hinders the
observation of its Raman signal because a cross section of Raman
scattering is extremely smaller than a cross section of the fluorescence.
In the Ag-CNT grid and the Ag--SiO2-CNT grid, smaller interparticle
gaps formed among the silver particles can improve the electromagnetic
enhancement of the two substrates. Thus, both the cross section of the
Raman scattering and the cross section of fluorescence can be increased.
If the interparticle gap is small enough, the cross section of the Raman
scattering can become comparable to or even larger than the cross section
of the fluorescence. Therefore, obvious Raman peaks can be detected with
the fluorescence spectrum. In experimental studies, a fluorescence quench
of the R6G has often been observed because of a rapid energy transfer
from excited electronic state to a surface of the metallic particles. In
FIG. 13, the fluorescence of R6G is quenched to a low and steady state
for the Ag-CNT grid, while the Raman signals on the Ag--SiO2-CNT
grid obviously superpose above a board fluorescence background. An
effective way of charge transfer can be provided because of the silver
film and the carbon nanotubes in Ag-CNT grid. The charge transfer can be
helpful for the quench of R6G fluorescence. In contract, the silicon
dioxide layer between the silver film and carbon nanotubes can evidently
prevent the charge transfer, thus the quench of R6G fluorescence cannot
be realized.

[0049]Referring to FIG. 14 of an embodiment, a Raman detecting system 200
includes a projecting module 210, an SERS substrate 220, and a receiving
module 230. The projecting module 210 can be configured to project a beam
of light to the SERS substrate 220 to form a scattering light. The SERS
substrate 220 is configured to load the sample. The receiving module 230
is configured to collect the scattering light scatted by the SERS
substrate 230 to form a Raman spectra figure.

[0050]Referring to FIG. 14 and FIG. 15, the SERS substrate 220 can include
a supporting element 221 and a carbon nanotube composite film 222
supported by the supporting element 221. The supporting element 221 can
be a transparent substrate such as a glass panel or a plastic substrate.
The carbon nanotube composite film 222 can include a carbon nanotube film
structure and a metallic film disposed on the carbon nanotube film
structure. The carbon nanotube film structure can include a plurality of
carbon nanotubes substantially perpendicular to a surface of the
supporting element 221. The carbon nanotubes can be single-walled carbon
nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), or
multi-walled carbon nanotubes (MWCNTs). The carbon nanotubes of the
carbon nanotube film are substantially parallel to each other and
approximately perpendicular to the transparent substrate to form a
super-aligned array. Heights of the carbon nanotubes can be substantially
equal to each other. The carbon nanotubes in the super-aligned array are
closely packed together by the van der Waals attractive force.

[0051]The compositions, features and functions of the Raman detecting
system 200 in the embodiment shown in FIG. 14 are similar to the Raman
detecting system 100 in the embodiment shown in FIG. 1. The difference is
that the carbon nanotubes of the carbon nanotube film structure of the
carbon nanotube composite film 222 are substantially perpendicular to a
surface of the supporting element 221. The metallic film can be disposed
on a surface of the carbon nanotube film structure opposite to the
supporter element 221. Microscopically, the metallic film can include a
plurality of metallic particles 222a. The metallic particle 222a can have
a diameter of about 10 nanometers to about 50 nanometers. The metallic
particles 222a can be disposed on distal ends of the carbon nanotubes as
shown in FIG. 15.

[0052]To test a Raman-enhancing capability of the SERS substrate 220
including the MWCNTs, an Ag-MWCNT array and a MWCNT array can be
provided. The Ag-MWCNT array can include a carbon nanotube film structure
consisting of MWCNTs and a silver film disposed on the carbon nanotube
film structure. The silver film can have a thickness of about 13
nanometers to about 17 nanometers. The MWCNT array can include a carbon
nanotube film structure consisting of MWCNTs. A droplet of R6G ethanol
solution can be used to slightly soak the surfaces of the Ag-MWCNT array
and the MWCNT array. As shown in FIG. 16, Raman spectrum for the MWCNT
gird cannot present the details of vibration modes of Rhodamine 6G (R6G)
with very low intensity. In contrast, details and highly enhanced Raman
peaks can be observed for Rhodamine 6G adsorbed on the Ag-MWCNT array.

[0053]To test a Raman-enhancing capability of the SERS substrate 220
including the SWCNTs, two Ag-SWCNT arrays and an SWCNT array can be
provided. Each of the two Ag-SWCNT arrays can include a carbon nanotube
film structure consisting of SWCNTs and a silver film disposed on the
carbon nanotube film structure. The silver film of one Ag-SWCNT arrays
can have a thickness of about 13 nanometers to about 17 nanometers. The
silver film of the other one of the two Ag-SWCNT arrays can have a
thickness of about 28 nanometers to about 32 nanometers. The SWCNT array
can include a carbon nanotube film structure consisting of SWCNTs. A
droplet of R6G ethanol solution can be used to slightly soak the surfaces
of the two Ag-SWCNT arrays and the SWCNT array respectively. As shown in
FIG. 17, Raman spectrum for the SWCNT gird cannot present the details of
vibration modes of R6G with very low intensity. In contrast, details and
highly enhanced Raman peaks can be observed for R6G adsorbed on two
Ag-SWCNT arrays.

[0054]Finally, it is to be understood that the above-described embodiments
are intended to illustrate rather than limit the disclosure. Variations
may be made to the embodiments without departing from the spirit of the
disclosure as claimed. Elements associated with any of the above
embodiments are envisioned to be associated with any other embodiments.
The above-described embodiments illustrate the scope of the disclosure
but do not restrict the scope of the disclosure.